WO2023039939A1 - Nano zirconium phosphate-based flame-retardant bacteriostatic agent and intumescent fireproof antibacterial coating prepared therefrom - Google Patents

Nano zirconium phosphate-based flame-retardant bacteriostatic agent and intumescent fireproof antibacterial coating prepared therefrom Download PDF

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WO2023039939A1
WO2023039939A1 PCT/CN2021/120989 CN2021120989W WO2023039939A1 WO 2023039939 A1 WO2023039939 A1 WO 2023039939A1 CN 2021120989 W CN2021120989 W CN 2021120989W WO 2023039939 A1 WO2023039939 A1 WO 2023039939A1
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zirconium phosphate
retardant
nano
preparation
flame
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French (fr)
Chinese (zh)
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刘治田
王成
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武汉工程大学
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C09D5/185—Intumescent paints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/322—Ammonium phosphate
    • C08K2003/323—Ammonium polyphosphate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/328—Phosphates of heavy metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Definitions

  • the invention belongs to the technical field of flame-retardant and antibacterial materials, and in particular relates to a nano-zirconium phosphate-based flame-retardant and antibacterial agent and an intumescent fire-proof and antibacterial coating prepared therefrom.
  • Intumescent fire retardant coating belongs to a kind of material that is coated on the surface of the substrate to improve its fire resistance and slow down the burning rate. It mainly uses polymer water-based emulsion, polymer resin, etc. It is prepared from an intumescent fireproof system composed of equal components, as well as functional fillers and corresponding additives. These components react at high temperature to produce a synergistic effect, dehydration and carbonization to form a uniform and dense honeycomb-shaped expanded carbon layer, which can effectively isolate air and heat transfer, thereby achieving excellent fire and heat insulation effects.
  • traditional fire retardant coatings usually have problems such as loose charcoal layer, resulting in poor flame retardant efficiency and almost no antibacterial effect.
  • Zirconium phosphate is a layered solid acid that can be synthesized artificially. It has excellent thermal stability, chemical stability and strong acid and alkali resistance.
  • the zirconium phosphate layer and the layer are mainly through hydrogen bonding and van der Waals force superposition.
  • the H + in the HP0 4 2- group has a large free mobility in the inner space of the layer, and the crystal water molecules between the layers can be polarized.
  • zirconium phosphate can significantly improve the flame retardancy of flame retardants based on its layered barrier effect and solid acid catalyzed char formation, but because the carbon layer of the traditional flame retardant system is relatively loose, zirconium phosphate is easy to agglomerate, resulting in retardation.
  • the combustion agent has problems such as poor thermal stability and low flame retardant efficiency.
  • the main purpose of the present invention is to provide a nano zirconium phosphate-based flame retardant and bacteriostatic agent and an intumescent fire retardant prepared by using it to solve the problems of poor charring quality, loose charcoal layer and low flame retardant efficiency of existing flame retardants.
  • Bacterial coating use aminoimidazole and chlorpropionaldehyde to modify the peeled zirconium phosphate nanosheets to synthesize a flame-retardant and antibacterial agent based on nano-zirconium phosphate, and use the Schiff base group formed by the reaction of aminoimidazole and chlorpropionaldehyde
  • the antibacterial performance of the fireproof coating is significantly improved; at the same time, the grafted imidazole group and zirconium phosphate have an excellent flame retardant synergistic effect, which can effectively improve the fireproof performance of the fireproof coating;
  • the flame retardant integrates flame-retardant, smoke-, smoke-, and bacteriostatic properties and enhanced functions, and involves a simple preparation method, low cost, environmental protection, wide applicability, and is suitable for popularization and application.
  • a preparation method of nano-zirconium phosphate-based flame retardant and antibacterial agent comprising the steps of:
  • ZrP Stripping zirconium phosphate: add tetrabutylammonium hydroxide dropwise to the zirconium phosphate dispersion (TBA can weaken the interlayer force of zirconium phosphate, peel off zirconium phosphate, and expose interlayer hydroxyl groups), carry out ultrasonic stirring reaction, and then drop Add concentrated acid to carry out secondary reaction (remove the above-mentioned TBA solution), carry out solid-liquid separation, and obtain translucent gel precipitation;
  • the zirconium phosphate is ⁇ -zirconium phosphate.
  • the concentrated acid is one or more of concentrated phosphoric acid, concentrated hydrochloric acid, concentrated nitric acid, and concentrated sulfuric acid; its concentration is 3-18 mol/L; the dropping time is 30-90 minutes.
  • the concentration of the tetrabutylammonium hydroxide solution is 0.05-10mol/L; the dropping time is 30-90min; the reaction temperature is 0-20°C; the ultrasonic stirring reaction time is 0.5-2h.
  • the molar ratio of zirconium phosphate introduced in step 1) to tetrabutylammonium hydroxide is 5:1-1:6.
  • the molar ratio of the tetrabutylammonium hydroxide to the acid component introduced by the concentrated acid is 2:1-1 :8.
  • the secondary reaction time in the step 1) is 0.5-3 hours.
  • the molar ratio of the zirconium phosphate introduced in the step 1), the chloropropionaldehyde introduced in the step 2) and the aminoimidazole introduced in the step 3) is 1:(1 ⁇ 8):(0.5 ⁇ 8 ).
  • the stirring reaction temperature in step 2) is 30-100°C, and the stirring time is 12-24h.
  • the aminoimidazole described in step 3 is an imidazole derivative containing an amino group, and 2-aminoimidazole, 4-aminoimidazole, 1-(3-aminopropyl)imidazole, 2-aminobenzo One or more of imidazole, etc.
  • the mechanical stirring temperature in step 3 is 60-120°C
  • the mechanical stirring time is 30-120min
  • the reflux reaction time is 12-24h.
  • the nano-zirconium phosphate-based flame retardant and antibacterial agent prepared according to the above scheme is light yellow powder crystal.
  • the nano-zirconium phosphate-based flame retardant and antibacterial agent obtained by the above scheme is applied to the preparation of intumescent fireproof coatings.
  • the components and their mass percentages include: methacrylic acid modified acrylate core-shell emulsion 20-30%, ammonium polyphosphate 30-36%, pentaerythritol 10-20%, melamine 10-15%, titanium dioxide 1-5%, hydroxyethyl cellulose 0.5-1%, dispersant 0.5-1%, defoamer 0.5-1%, n-octyl 0.5-1% of alcohol, 1-10% of nano-zirconium phosphate-based flame retardant and antibacterial agent, and the rest is water.
  • the intumescent fireproof coating prepared according to the above scheme has excellent fire resistance, good antibacterial effect, low halogen-free cost, environmental protection and wide applicability.
  • tetrabutylammonium hydroxide is used to strip zirconium phosphate firstly, and the hydroxyl group between the zirconium phosphate layers is exposed, and then chloropropionaldehyde is used to chemically react with the peeled zirconium phosphate, and finally aminoimidazole is reacted with the aldehyde group in chloropropionaldehyde
  • the Schiff base is formed, and the nano-zirconium phosphate-based flame retardant and antibacterial agent is prepared.
  • Combustion gas blows the charcoal layer to form a honeycomb porous carbon layer to play a flame-retardant effect; while the nano-zirconium phosphate-based flame-retardant and antibacterial agent obtained in the present invention can quickly form charcoal on the surface of the substrate while exerting a flame-retardant effect, Fill the gap between the sheets, form more and dense microscopic carbon cages, block the oxygen and heat transfer in the air, and seal a large number of degradation products in it, and the introduced Schiff base and aminoimidazole can act In the microscopic carbon cage, zirconium phosphate reacts with chloropropionaldehyde and aminoimidazole to cross-link to produce a cross-linked network structure with high thermal stability, thereby improving the degree of graphitization of the burning carbon layer, achieving a P-N-C synergistic effect, and effectively improving the carbon density.
  • the strength of the carbon layer of the cage can enhance the compactness of the carbon layer, and further play a flame-retardant effect on the microstructure level, and play a synergistic flame-retardant effect with the intumescent flame-retardant system in the fire-resistant coating; in addition, the obtained organically modified nano-zirconium phosphate has It is beneficial to simultaneously improve the durability of fire retardant coatings.
  • the present invention utilizes the antibacterial ability of the high-valent metal zirconium ions of nano-zirconium phosphate.
  • the nano-sized zirconium phosphate nanoparticle size and the zirconium ions therein can destroy the cell wall of microorganisms, and impel the Schiff base and imidazole, etc.
  • the group exerts its effect inside the cell, which can effectively improve the antibacterial effect of the Schiff base, and the imidazole group can play a better antibacterial synergistic effect with the Schiff base. Multiple mechanisms work together to significantly improve the antibacterial effect of the obtained coating. bacteria performance.
  • the nano-zirconium phosphate-based flame retardant and antibacterial agent of the present invention has high-efficiency flame retardancy and excellent char formation, and can play a synergistic flame retardant effect with the intumescent fireproof system composed of ammonium polyphosphate, pentaerythritol and melamine in fireproof coatings , to promote the formation of a carbon layer with higher quality and strength in the fire retardant coating, thereby achieving more efficient flame retardancy; at the same time, based on the Schiff base group in the flame retardant and antibacterial agent and the unique synergistic antibacterial effect between zirconium phosphate and imidazole, The antibacterial effect of the fireproof coating can be simultaneously improved; the obtained flame retardant integrates flame retardancy, smoke suppression, antibacterial and enhancement functions, and can take into account good chemical stability, and can effectively expand the application field of the fireproof coating.
  • Using chlorpropionaldehyde and aminoimidazole to graft and modify the zirconium phosphate layer can effectively reduce the surface polarity of zirconium phosphate, effectively simplify the composition of the fireproof coating, and improve the compatibility and dispersion of the components of the coating More preferably, it can effectively improve the film-forming property, fire resistance, durability and practicality of the paint, and further effectively improve the fire performance of the obtained fire retardant paint.
  • the nano-zirconium phosphate-based flame retardant and antibacterial agent of the present invention utilizes the contact reaction mechanism and the active oxygen mechanism to destroy the replication ability of the DNA molecule of bacteria, thereby affecting the normal replication of genetic material and the reproduction of organisms; base, which further oxidizes the outer membrane of the cell to kill the microorganism; the tiny particle size of nano-zirconium phosphate can load imidazole and Schiff base groups to attack microorganisms more easily, and combine with the sulfhydryl group of the enzyme protein in the cell, making some enzymes containing sulfhydryl groups Lose activity, destroy the cell wall of microorganisms, inhibit the growth and reproduction of microorganisms, and achieve excellent antibacterial effects.
  • the halogen-free flame retardant obtained in the present invention has low cost, good char formation, environmental friendliness and wide applicability, the preparation method involved is simple and convenient, the reaction conditions are mild, the application fields are wide, and it is suitable for industrialization and popularization and application.
  • the preparation method of the zirconium phosphate ( ⁇ -zirconium phosphate) used comprises the following steps: preparing 50 mL of concentrated phosphoric acid with a molar concentration of 1 mol/L, adding it to a 250 ml three-necked flask, and then adding 5.00 g of zirconium oxychloride (ZrOCl 2 -8H 2 0), heat up to 95°C, mechanically stir for 20 minutes to fully disperse zirconium oxychloride and stop stirring, react at reflux temperature for 24 hours, after the reaction, carry out solid-liquid separation, and wash the obtained solid product with an appropriate amount of deionized water Wash until the centrifugal supernatant satisfies pH>5, and dry the washed solid product in an oven at 80° C. for 12 hours, and grind to obtain a white powder of zirconium phosphate.
  • the dispersant used is wetting and dispersing agent 5040, and the defoamer is silicone defoamer 470.
  • the preparation method of the methacrylic acid-modified acrylate emulsion that adopts comprises the steps:
  • Shell polymerization At the end of the heat preservation of the core emulsion, add the remaining initiator aqueous solution and shell pre-emulsion dropwise, and finish the drop within 1.5 hours, then raise the temperature to 85°C and keep it for 0.5h, and then naturally cool to 40°C. Adjust the pH value to 8 and pass through a 200-mesh sieve to obtain a methacrylic acid-modified acrylate core-shell emulsion.
  • a kind of nano-zirconium phosphate-based flame retardant antibacterial agent, its preparation method comprises the steps:
  • ZrP Stripping zirconium phosphate
  • step 3 Synthesis of Schiff base: Disperse the product obtained in step 2) and 0.01mol aminoimidazole in DMSO, mechanically stir at 80°C for 60min, then heat to reflux for 24h, after the reaction, cool to room temperature, filter, wash, A flame retardant and antibacterial agent based on nanometer zirconium phosphate can be obtained.
  • a kind of nano-zirconium phosphate-based flame retardant antibacterial agent, its preparation method comprises the steps:
  • ZrP Stripping zirconium phosphate
  • step 3 Synthesis of Schiff base: Disperse the product obtained in step 2) and 0.01mol aminoimidazole in DMSO, mechanically stir at 70°C for 90min, heat to reflux for 18h, after the reaction is completed, cool to room temperature, filter, and wash, that is A flame retardant and antibacterial agent based on nano zirconium phosphate can be obtained.
  • the nano-zirconium phosphate-based flame retardant and antibacterial agent obtained in Example 1 is applied to the preparation of intumescent fireproof coatings.
  • the components and their mass percentages are: 20% of methacrylic acid modified acrylate emulsion, 36% of ammonium polyphosphate, 12% pentaerythritol, 12% melamine, 3% titanium dioxide, 0.5% hydroxyethyl cellulose, 0.5% dispersant, 0.5% defoamer, 0.5% n-octanol, 10% water, flame retardant and antibacterial based on nano zirconium phosphate 5% agent; grind the weighed flame retardant and antibacterial agent based on nano-zirconium phosphate, ammonium polyphosphate, pentaerythritol, melamine, titanium dioxide, and hydroxyethyl cellulose into powder, then add water to fully grind and mix evenly; then add defoaming agent and dispersant, and continue to grind thoroughly; finally, add methacryl
  • the nano-zirconium phosphate-based flame retardant and antibacterial agent obtained in Example 1 is applied to the preparation of intumescent fireproof coatings.
  • the components and their mass percentages are: 20% of methacrylic acid modified acrylate emulsion, 36% of ammonium polyphosphate, Pentaerythritol 12%, melamine 12%, titanium dioxide 3%, hydroxyethyl cellulose 0.5%, dispersant 0.5%, defoamer 0.5%, n-octanol 0.5%, water 12%, flame retardant and antibacterial based on nano zirconium phosphate 3%; Grind the weighed flame retardant and antibacterial agent based on nano-zirconium phosphate, ammonium polyphosphate, pentaerythritol, melamine, titanium dioxide, and hydroxyethyl cellulose into powder, then add water to fully grind and mix evenly; then add defoaming agent and dispersant, and continue to grind thoroughly; finally, add meth
  • the nano-zirconium phosphate-based flame retardant and antibacterial agent obtained in Example 1 is applied to the preparation of intumescent fireproof coatings.
  • the components and their mass percentages are: 20% of methacrylic acid modified acrylate emulsion, 36% of ammonium polyphosphate, Pentaerythritol 12%, melamine 12%, titanium dioxide 3%, hydroxyethyl cellulose 0.5%, dispersant 0.5%, defoamer 0.5%, n-octanol 0.5%, water 13%, flame retardant and antibacterial based on nano zirconium phosphate 2%; Grind the weighed flame retardant and antibacterial agent based on nano-zirconium phosphate, ammonium polyphosphate, pentaerythritol, melamine, titanium dioxide, and hydroxyethyl cellulose into powder, then add water to fully grind and mix evenly; then add defoaming agent and dispersant, and continue to grind thoroughly; finally, add meth
  • the preparation method of the fireproof coating described in Comparative Example 1 is roughly the same as Application Example 1, except that each component and its mass percentage are: 20% of methacrylic acid modified acrylate emulsion, 36% of ammonium polyphosphate, pentaerythritol 12%, melamine 12%, titanium dioxide 3%, hydroxyethyl cellulose 0.5%, dispersant 0.5%, defoamer 0.5%, n-octanol 0.5%, water 15%.
  • the preparation method of the fireproof coating described in Comparative Example 2 is roughly the same as that of Application Example 1, except that each component and its mass percentage are: 20% of methacrylic acid modified acrylate emulsion, 36% of ammonium polyphosphate, pentaerythritol 12%, melamine 12%, titanium dioxide 3%, hydroxyethyl cellulose 0.5%, dispersant 0.5%, defoamer 0.5%, n-octanol 0.5%, water 10%, zirconium phosphate 5%.
  • the preparation method of the fireproof coating described in Comparative Example 3 is roughly the same as that of Application Example 1, except that each component and its mass percentage are: 20% of methacrylic acid modified acrylate emulsion, 36% of ammonium polyphosphate, pentaerythritol 12%, melamine 12%, titanium dioxide 3%, hydroxyethyl cellulose 0.5%, dispersant 0.5%, defoamer 0.5%, n-octanol 0.5%, water 10%, 2-aminoimidazole 5%.
  • the preparation method of the fireproof coating described in Comparative Example 4 is roughly the same as that of Application Example 1, except that each component and its mass percentage are: 20% of methacrylic acid modified acrylate emulsion, 36% of ammonium polyphosphate, pentaerythritol 12%, melamine 12%, titanium dioxide 3%, hydroxyethyl cellulose 0.5%, dispersant 0.5%, defoamer 0.5%, n-octanol 0.5%, water 10%, zirconium phosphate and 2-aminoimidazole mixture 5wt % (zirconium phosphate 3wt%, 2-aminoimidazole 2wt%).
  • the flame retardant and bacteriostatic agent based on nano-zirconium phosphate of the present invention has high flame retardant efficiency, excellent bacteriostatic effect, environmental protection and pollution-free, good compatibility with resins, substrates, etc., and can effectively take into account
  • Other properties of the material, when applied to the preparation of intumescent fireproof coatings can show the advantages of excellent fire resistance, good antibacterial performance, good char formation, high carbon layer strength, good stability (long storage time), etc., and
  • the involved preparation method is simple and has wide application fields.

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Abstract

Disclosed in the present invention is a nano zirconium phosphate-based flame-retardant bacteriostatic agent. Intercalation stripping is performed on zirconium phosphate first, and zirconium phosphate is modified by using aminoimidazole and chloropropionaldehyde to prepare a flame-retardant bacteriostatic agent based on nano zirconium phosphate capable of playing a synergistic flame-retardant role with an intumescent flame-retardant system in a fireproof coating while effectively solving problems such as easy agglomeration of zirconium phosphate, and remarkably improving the film-forming properties, fire resistance and durability of the obtained fireproof coating. Schiff base and imidazole loaded on the surface of a nano zirconium phosphate layer can be more uniformly dispersed in coating components, so that a barrier bacteriostatic effect is achieved, and Schiff base, nano zirconium phosphate and imidazole in the flame retardant can effectively improve the antibacterial properties of the fireproof coating. The flame retardant obtained in the present invention integrates flame retardance, smoke suppression, bacteriostasis and enhancement functions, and is low in halogen-free cost, good in char forming properties, environment-friendly, and wide in applicability, and a related preparation method is simple in process, simple in reaction conditions and suitable for popularization and application.

Description

一种纳米磷酸锆基阻燃抑菌剂及其制备的膨胀型防火抑菌涂料A nano-zirconium phosphate-based flame retardant and antibacterial agent and the intumescent fireproof and antibacterial coating prepared therefrom 技术领域technical field
本发明属于阻燃抑菌材料技术领域，具体涉及一种纳米磷酸锆基阻燃抑菌剂及其制备的膨胀型防火抑菌涂料。The invention belongs to the technical field of flame-retardant and antibacterial materials, and in particular relates to a nano-zirconium phosphate-based flame-retardant and antibacterial agent and an intumescent fire-proof and antibacterial coating prepared therefrom.
背景技术Background technique
膨胀型防火涂料属于一种涂覆在基材表面提高其耐火能力、减缓燃烧速率的一类物质，主要以高分子水性乳液、高分子树脂等作为基体，加入由酸源、气源和碳源等组成的膨胀防火体系以及功能填料和相应助剂制备而成。这些组分在高温下发生反应，产生协同作用，脱水碳化形成均匀致密的蜂窝状膨胀炭层，可有效隔绝空气和热量传递，从而达到优异的防火隔热的效果。但是传统防火涂料通常存在炭层疏松等问题，导致阻燃效率不佳，同时几乎没有抑菌效果。Intumescent fire retardant coating belongs to a kind of material that is coated on the surface of the substrate to improve its fire resistance and slow down the burning rate. It mainly uses polymer water-based emulsion, polymer resin, etc. It is prepared from an intumescent fireproof system composed of equal components, as well as functional fillers and corresponding additives. These components react at high temperature to produce a synergistic effect, dehydration and carbonization to form a uniform and dense honeycomb-shaped expanded carbon layer, which can effectively isolate air and heat transfer, thereby achieving excellent fire and heat insulation effects. However, traditional fire retardant coatings usually have problems such as loose charcoal layer, resulting in poor flame retardant efficiency and almost no antibacterial effect.
磷酸锆是一种可人工合成的层状固体酸，具有优异的热稳定性、化学稳定性和耐强酸强碱性能等特点。磷酸锆层与层之间主要通过氢键作用及范德华力叠加，其HP0 4 2-基团中的H +在层内空间具有较大的自由活动性，其层间结晶水分子可以被极性有机分子替代。尽管磷酸锆基于其层状阻隔作用和固体酸催化成炭作用，可较为明显地提升阻燃剂的阻燃性，但是由于传统的阻燃体系炭层较为疏松，磷酸锆易团聚，从而导致阻燃剂存在热稳定性较差、阻燃效率较低等问题。 Zirconium phosphate is a layered solid acid that can be synthesized artificially. It has excellent thermal stability, chemical stability and strong acid and alkali resistance. The zirconium phosphate layer and the layer are mainly through hydrogen bonding and van der Waals force superposition. The H + in the HP0 4 2- group has a large free mobility in the inner space of the layer, and the crystal water molecules between the layers can be polarized. Organic molecular substitution. Although zirconium phosphate can significantly improve the flame retardancy of flame retardants based on its layered barrier effect and solid acid catalyzed char formation, but because the carbon layer of the traditional flame retardant system is relatively loose, zirconium phosphate is easy to agglomerate, resulting in retardation. The combustion agent has problems such as poor thermal stability and low flame retardant efficiency.
为解决上述技术问题，对磷酸锆进行有机表面改性是一种常用且有效的方法。专利CN108203519A中采用甲胺对磷酸锆进行插层，经机械球磨后剥离成片层磷酸锆，同时将片层磷酸锆与大分子阻燃剂MCA进行混合，将磷酸锆作为协效剂改性阻燃剂，应用在PA6阻燃复合材料中，但该专利中仅将磷酸锆作为协效剂，而且只针对PA6材料，存在复配量较大、应用领域受到限制，阻燃效果不佳等问题。专利CN109810545A中将磷酸锆剥离成纳米片加入到阻燃体系中，通过磷酸锆纳米片的催化作用，提高聚合物成炭作用，进而提升阻燃效率，不过该专利中仅将磷酸锆剥离，利用纳米片磷酸锆在体系中分散，但并未解决磷酸锆纳米片容易出现团聚现象，导致了磷酸锆的催化成炭作用不能有效释放，同时也并未考虑与树脂相容性问题，导致其阻燃效率仍不太理想。除此之外，磷酸锆对于涂料的抑菌效果鲜少有专利报道。In order to solve the above technical problems, organic surface modification of zirconium phosphate is a commonly used and effective method. In patent CN108203519A, methylamine is used to intercalate zirconium phosphate, and after mechanical ball milling, zirconium phosphate is peeled off into lamellar zirconium phosphate. Flame-retardant, used in PA6 flame-retardant composite materials, but only zirconium phosphate is used as a synergist in this patent, and only for PA6 materials, there are problems such as large compounding amount, limited application fields, and poor flame-retardant effect . In patent CN109810545A, zirconium phosphate is stripped into nanosheets and added to the flame retardant system. Through the catalytic action of zirconium phosphate nanosheets, the charring effect of the polymer is improved, thereby improving the flame retardant efficiency. However, in this patent, only zirconium phosphate is stripped and used Nanosheet zirconium phosphate is dispersed in the system, but it does not solve the problem that zirconium phosphate nanosheets are prone to agglomeration, which leads to the ineffective release of the catalytic charring effect of zirconium phosphate. Fuel efficiency is still not ideal. In addition, there are few patent reports on the antibacterial effect of zirconium phosphate on coatings.
因此，进一步优化磷酸锆类化合物的改性手段及提升其相关性能的应用领域具有重大研究和应用意义。Therefore, it is of great research and application significance to further optimize the modification methods of zirconium phosphate compounds and the application fields to improve their related properties.
发明内容Contents of the invention
本发明的主要目的在于针对现有阻燃剂成炭质量不佳、炭层松散以及阻燃效率低等问题， 提供一种纳米磷酸锆基阻燃抑菌剂及利用其制备的膨胀型防火抑菌涂料；利用氨基咪唑和氯丙醛对剥离后的磷酸锆纳米片进行修饰，合成一种基于纳米磷酸锆的阻燃抑菌剂，利用氨基咪唑和氯丙醛反应形成的希夫碱基团以及磷酸锆和咪唑的特有的协同抗菌效果，使防火涂料的抑菌性能显著提高；同时接枝的咪唑基团与磷酸锆具有优异的阻燃协同效果，可有效提高防火涂料的防火性能；所得阻燃剂集阻燃抑烟抑菌性能与增强功能于一体，且涉及的制备方法简单，成本低，环保，适用性广泛，适合推广应用。The main purpose of the present invention is to provide a nano zirconium phosphate-based flame retardant and bacteriostatic agent and an intumescent fire retardant prepared by using it to solve the problems of poor charring quality, loose charcoal layer and low flame retardant efficiency of existing flame retardants. Bacterial coating; use aminoimidazole and chlorpropionaldehyde to modify the peeled zirconium phosphate nanosheets to synthesize a flame-retardant and antibacterial agent based on nano-zirconium phosphate, and use the Schiff base group formed by the reaction of aminoimidazole and chlorpropionaldehyde As well as the unique synergistic antibacterial effect of zirconium phosphate and imidazole, the antibacterial performance of the fireproof coating is significantly improved; at the same time, the grafted imidazole group and zirconium phosphate have an excellent flame retardant synergistic effect, which can effectively improve the fireproof performance of the fireproof coating; The flame retardant integrates flame-retardant, smoke-, smoke-, and bacteriostatic properties and enhanced functions, and involves a simple preparation method, low cost, environmental protection, wide applicability, and is suitable for popularization and application.
为实现上述目的，本发明采用的技术方案为：To achieve the above object, the technical solution adopted in the present invention is:
一种纳米磷酸锆基阻燃抑菌剂的制备方法，包括如下步骤：A preparation method of nano-zirconium phosphate-based flame retardant and antibacterial agent, comprising the steps of:
1)剥离磷酸锆(ZrP)：向磷酸锆分散液中滴加四丁基氢氧化铵(TBA可以减弱磷酸锆层间作用力，剥离磷酸锆，暴露出层间羟基)，进行超声搅拌反应，然后滴加浓酸进行二次反应(去除上述TBA溶液)，进行固液分离，得半透明凝胶沉淀；1) Stripping zirconium phosphate (ZrP): add tetrabutylammonium hydroxide dropwise to the zirconium phosphate dispersion (TBA can weaken the interlayer force of zirconium phosphate, peel off zirconium phosphate, and expose interlayer hydroxyl groups), carry out ultrasonic stirring reaction, and then drop Add concentrated acid to carry out secondary reaction (remove the above-mentioned TBA solution), carry out solid-liquid separation, and obtain translucent gel precipitation;
2)接枝氯丙醛：将步骤1)所得半透明凝胶沉淀与氯丙醛混合，进行搅拌反应，离心洗涤后，干燥，得淡黄色液体；2) Grafting chlorpropionaldehyde: mixing the translucent gel precipitate obtained in step 1) with chlorpropionaldehyde, stirring and reacting, centrifuging and washing, drying to obtain a light yellow liquid;
3)合成希夫碱：将步骤2)所得淡黄色液体与氨基咪唑混合，在一定温度下进行机械搅拌，加热至回流，反应结束后，冷却至室温，过滤，洗涤，即得所述基于纳米磷酸锆的阻燃抑菌剂。3) Synthesis of Schiff base: Mix the light yellow liquid obtained in step 2) with aminoimidazole, mechanically stir at a certain temperature, and heat to reflux. After the reaction is completed, cool to room temperature, filter, and wash to obtain the nano-based Flame retardant and bacteriostatic agent of zirconium phosphate.
上述方案中，所述磷酸锆为α-磷酸锆。In the above scheme, the zirconium phosphate is α-zirconium phosphate.
上述方案中，所述浓酸为浓磷酸、浓盐酸、浓硝酸、浓硫酸中的一种或几种；其浓度为3～18mol/L；滴加时间为30～90min。In the above scheme, the concentrated acid is one or more of concentrated phosphoric acid, concentrated hydrochloric acid, concentrated nitric acid, and concentrated sulfuric acid; its concentration is 3-18 mol/L; the dropping time is 30-90 minutes.
上述方案中，所述四丁基氢氧化铵溶液的浓度为0.05-10mol/L；滴加时间为30-90min；反应温度为0～20℃；超声搅拌反应时间为0.5～2h。In the above scheme, the concentration of the tetrabutylammonium hydroxide solution is 0.05-10mol/L; the dropping time is 30-90min; the reaction temperature is 0-20°C; the ultrasonic stirring reaction time is 0.5-2h.
上述方案中，步骤1)中引入的磷酸锆与四丁基氢氧化铵的摩尔比为5:1～1:6。In the above scheme, the molar ratio of zirconium phosphate introduced in step 1) to tetrabutylammonium hydroxide is 5:1-1:6.
上述方案中，所述四丁基氢氧化铵与浓酸引入的酸组分(H 3PO 4、HCl、HNO 3、H 2SO 4中的一种或几种)的摩尔比为2:1～1:8。 In the above scheme, the molar ratio of the tetrabutylammonium hydroxide to the acid component introduced by the concentrated acid (one or more of H 3 PO 4 , HCl, HNO 3 , H 2 SO 4 ) is 2:1-1 :8.
上述方案中，所述步骤1)中所述二次反应时间为0.5～3h。In the above scheme, the secondary reaction time in the step 1) is 0.5-3 hours.
上述方案中，所述步骤1)中引入的磷酸锆、步骤2)中引入的氯丙醛与步骤3)中引入的氨基咪唑的的摩尔比为1:(1～8):(0.5～8)。In the above scheme, the molar ratio of the zirconium phosphate introduced in the step 1), the chloropropionaldehyde introduced in the step 2) and the aminoimidazole introduced in the step 3) is 1:(1～8):(0.5～8 ).
上述方案中，步骤2)中所述搅拌反应温度为30-100℃，搅拌时间为12～24h。In the above scheme, the stirring reaction temperature in step 2) is 30-100°C, and the stirring time is 12-24h.
上述方案中，步骤3)中所述的氨基咪唑为含有氨基的咪唑类衍生物，可选用2-氨基咪唑、4-氨基咪唑、1-(3-氨基丙基)咪唑、2-氨基苯并咪唑等中的一种或几种。In the above scheme, the aminoimidazole described in step 3) is an imidazole derivative containing an amino group, and 2-aminoimidazole, 4-aminoimidazole, 1-(3-aminopropyl)imidazole, 2-aminobenzo One or more of imidazole, etc.
上述方案中，步骤3)中所述机械搅拌温度为60～120℃，机械搅拌时间为30-120min，回流 反应时间为12～24h。In the above scheme, the mechanical stirring temperature in step 3) is 60-120°C, the mechanical stirring time is 30-120min, and the reflux reaction time is 12-24h.
根据上述方案制备的纳米磷酸锆基阻燃抑菌剂为淡黄色粉末晶体。The nano-zirconium phosphate-based flame retardant and antibacterial agent prepared according to the above scheme is light yellow powder crystal.
将上述方案所得纳米磷酸锆基阻燃抑菌剂应用于制备膨胀型防火涂料，各组分及其所占质量百分比包括：甲基丙烯酸改性丙烯酸酯核壳乳液20～30％，聚磷酸铵30～36％，季戊四醇10～20％，三聚氰胺10～15％，二氧化钛1～5％，羟乙基纤维素0.5～1％，分散剂0.5～1％，消泡剂0.5～1％，正辛醇0.5～1％，纳米磷酸锆基阻燃抑菌剂1～10％，其余为水。The nano-zirconium phosphate-based flame retardant and antibacterial agent obtained by the above scheme is applied to the preparation of intumescent fireproof coatings. The components and their mass percentages include: methacrylic acid modified acrylate core-shell emulsion 20-30%, ammonium polyphosphate 30-36%, pentaerythritol 10-20%, melamine 10-15%, titanium dioxide 1-5%, hydroxyethyl cellulose 0.5-1%, dispersant 0.5-1%, defoamer 0.5-1%, n-octyl 0.5-1% of alcohol, 1-10% of nano-zirconium phosphate-based flame retardant and antibacterial agent, and the rest is water.
根据上述方案制备膨胀型防火涂料，其耐火性能优异，抑菌效果好，且无卤成本低，环保且适用性广泛。The intumescent fireproof coating prepared according to the above scheme has excellent fire resistance, good antibacterial effect, low halogen-free cost, environmental protection and wide applicability.
本发明的原理为：Principle of the present invention is:
本发明首先利用四丁基氢氧化铵对磷酸锆进行剥离，暴露磷酸锆层间的羟基，然后利用氯丙醛与剥离后的磷酸锆进行化学反应，最后通过氨基咪唑与氯丙醛中的醛基反应形成希夫碱，制备出纳米磷酸锆基阻燃抑菌剂，将其应用于膨胀型防火涂料体系可显著提升其防火性能和耐久性能，同时具有优异的抑菌效果：In the present invention, tetrabutylammonium hydroxide is used to strip zirconium phosphate firstly, and the hydroxyl group between the zirconium phosphate layers is exposed, and then chloropropionaldehyde is used to chemically react with the peeled zirconium phosphate, and finally aminoimidazole is reacted with the aldehyde group in chloropropionaldehyde The Schiff base is formed, and the nano-zirconium phosphate-based flame retardant and antibacterial agent is prepared. Applying it to the intumescent fireproof coating system can significantly improve its fireproof performance and durability, and has excellent antibacterial effect at the same time:
1)阻燃性能和耐久性能；在火灾发生时，聚磷酸铵在火灾高温下分解释放出酸性物质以及氨气等不可燃气体，并催化季戊四醇脱水碳化形成炭层骨架，最后三聚氰胺受热分解释放不可燃气体，吹鼓炭层，形成蜂窝状多孔碳层，发挥阻燃作用；而本发明所得纳米磷酸锆基阻燃抑菌剂在发挥阻燃作用的同时，可在基材表面快速成炭，填补片层与片层之间的空隙，形成较多而密集的微观碳笼，阻隔空气中的氧气以及热量传递，并将大量的降解产物封闭其中，同时引入的希夫碱以及氨基咪唑可作用于微观碳笼中，磷酸锆与氯丙醛和氨基咪唑反应可交联产生高热稳定性的交联网状结构，进而提升燃烧碳层的石墨化程度，可以实现P-N-C协同效应，同时可有效提高碳笼的碳层强度，增强炭层致密性，进一步在微观结构层面上发挥出阻燃作用，并与防火涂料中的膨胀阻燃体系发挥协同阻燃作用；此外，所得有机改性纳米磷酸锆有利于同步提升防火涂料的耐久性能。1) Flame retardancy and durability; when a fire occurs, ammonium polyphosphate decomposes and releases acidic substances and ammonia gas and other incombustible gases at high temperatures, and catalyzes the dehydration and carbonization of pentaerythritol to form a carbon layer skeleton. Finally, melamine is thermally decomposed and released. Combustion gas blows the charcoal layer to form a honeycomb porous carbon layer to play a flame-retardant effect; while the nano-zirconium phosphate-based flame-retardant and antibacterial agent obtained in the present invention can quickly form charcoal on the surface of the substrate while exerting a flame-retardant effect, Fill the gap between the sheets, form more and dense microscopic carbon cages, block the oxygen and heat transfer in the air, and seal a large number of degradation products in it, and the introduced Schiff base and aminoimidazole can act In the microscopic carbon cage, zirconium phosphate reacts with chloropropionaldehyde and aminoimidazole to cross-link to produce a cross-linked network structure with high thermal stability, thereby improving the degree of graphitization of the burning carbon layer, achieving a P-N-C synergistic effect, and effectively improving the carbon density. The strength of the carbon layer of the cage can enhance the compactness of the carbon layer, and further play a flame-retardant effect on the microstructure level, and play a synergistic flame-retardant effect with the intumescent flame-retardant system in the fire-resistant coating; in addition, the obtained organically modified nano-zirconium phosphate has It is beneficial to simultaneously improve the durability of fire retardant coatings.
2)本发明利用纳米磷酸锆的高价金属锆离子的抑菌能力，此外纳米磷酸锆纳米粒径及其中的锆离子可以破坏微生物的细胞壁，促使纳米磷酸锆片层负载的希夫碱及咪唑等基团进行细胞内部发挥效应，可有效提高希夫碱的抑菌效果，并且咪唑基团可以与希夫碱发挥较好的抑菌协同作用，多种机制共同作用，可显著提升所得涂料的抑菌性能。2) The present invention utilizes the antibacterial ability of the high-valent metal zirconium ions of nano-zirconium phosphate. In addition, the nano-sized zirconium phosphate nanoparticle size and the zirconium ions therein can destroy the cell wall of microorganisms, and impel the Schiff base and imidazole, etc. The group exerts its effect inside the cell, which can effectively improve the antibacterial effect of the Schiff base, and the imidazole group can play a better antibacterial synergistic effect with the Schiff base. Multiple mechanisms work together to significantly improve the antibacterial effect of the obtained coating. bacteria performance.
与现有技术相比，本发明的有益效果为：Compared with prior art, the beneficial effect of the present invention is:
1)本发明所述纳米磷酸锆基阻燃抑菌剂具有高效阻燃性和优异的成炭性，可与防火涂料中聚磷酸铵、季戊四醇、三聚氰胺所组成的膨胀防火体系发挥协同阻燃作用，促使防火涂料形成质量强度更高的碳层，进而实现更高效的阻燃性；同时基于该阻燃抑菌剂中的希夫碱基 团以及磷酸锆与咪唑之间特有的协同抗菌效果，可同步提高防火涂料的抑菌效果；所得阻燃剂集阻燃抑烟抑菌与增强功能于一体，并可兼顾良好的化学稳定性能，可有效拓展防火涂料的应用领域。1) The nano-zirconium phosphate-based flame retardant and antibacterial agent of the present invention has high-efficiency flame retardancy and excellent char formation, and can play a synergistic flame retardant effect with the intumescent fireproof system composed of ammonium polyphosphate, pentaerythritol and melamine in fireproof coatings , to promote the formation of a carbon layer with higher quality and strength in the fire retardant coating, thereby achieving more efficient flame retardancy; at the same time, based on the Schiff base group in the flame retardant and antibacterial agent and the unique synergistic antibacterial effect between zirconium phosphate and imidazole, The antibacterial effect of the fireproof coating can be simultaneously improved; the obtained flame retardant integrates flame retardancy, smoke suppression, antibacterial and enhancement functions, and can take into account good chemical stability, and can effectively expand the application field of the fireproof coating.
2)采用氯丙醛和氨基咪唑对磷酸锆片层进行接枝改性，可有效降低磷酸锆的表面极性，有效简化防火涂料组成成分，使涂料各组分之间相容性和分散性更佳，可有效提高涂料的成膜性、耐火性、耐久性和实用性，并进一步有效提升所得防火涂料的防火性能。2) Using chlorpropionaldehyde and aminoimidazole to graft and modify the zirconium phosphate layer can effectively reduce the surface polarity of zirconium phosphate, effectively simplify the composition of the fireproof coating, and improve the compatibility and dispersion of the components of the coating More preferably, it can effectively improve the film-forming property, fire resistance, durability and practicality of the paint, and further effectively improve the fire performance of the obtained fire retardant paint.
3)本发明所述纳米磷酸锆基阻燃抑菌剂利用接触反应机理和活性氧机理，破坏细菌的DNA分子的复制能力，从而影响遗传物质正常的复制及生物体的繁殖；可通过产生自由基，进一步氧化细胞外膜使微生物死亡；纳米磷酸锆的微小粒径，可以负载咪唑及希夫碱基团更易进攻微生物，并与细胞中酶蛋白的巯基结合，使一些含巯基基团的酶失去活性，破坏微生物的细胞壁，制微生物的生长繁殖，达到优异的抑菌效果等。3) The nano-zirconium phosphate-based flame retardant and antibacterial agent of the present invention utilizes the contact reaction mechanism and the active oxygen mechanism to destroy the replication ability of the DNA molecule of bacteria, thereby affecting the normal replication of genetic material and the reproduction of organisms; base, which further oxidizes the outer membrane of the cell to kill the microorganism; the tiny particle size of nano-zirconium phosphate can load imidazole and Schiff base groups to attack microorganisms more easily, and combine with the sulfhydryl group of the enzyme protein in the cell, making some enzymes containing sulfhydryl groups Lose activity, destroy the cell wall of microorganisms, inhibit the growth and reproduction of microorganisms, and achieve excellent antibacterial effects.
4)本发明所得阻燃剂无卤成本低，成炭性好，环保友好且适用性广泛，涉及的制备方法工艺简单方便，反应条件温和，应用领域广泛，适合工业化及推广应用。4) The halogen-free flame retardant obtained in the present invention has low cost, good char formation, environmental friendliness and wide applicability, the preparation method involved is simple and convenient, the reaction conditions are mild, the application fields are wide, and it is suitable for industrialization and popularization and application.
具体实施方式Detailed ways
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。In order to make the object, technical solution and advantages of the present invention more clear, the present invention will be further described in detail below in conjunction with the examples. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention.
以下实施例中，采用的磷酸锆(α-磷酸锆)的制备方法包括如下步骤：配制50mL摩尔浓度为1mo1/L的浓磷酸，加入250ml三口烧瓶中，再加入5.00g氧氯化锆(ZrOCl 2-8H 20)，升温到95℃，机械搅拌20min使氧氯化锆充分分散并停止搅拌，回流温度下反应24h，反应结束后，进行固液分离，将所得固体产物用适量去离子水洗涤，至离心清液满足pH>5，洗涤后的固体产物在80℃烘箱中干燥12h，研磨得到磷酸锆白色粉末。 In the following examples, the preparation method of the zirconium phosphate (α-zirconium phosphate) used comprises the following steps: preparing 50 mL of concentrated phosphoric acid with a molar concentration of 1 mol/L, adding it to a 250 ml three-necked flask, and then adding 5.00 g of zirconium oxychloride (ZrOCl 2 -8H 2 0), heat up to 95°C, mechanically stir for 20 minutes to fully disperse zirconium oxychloride and stop stirring, react at reflux temperature for 24 hours, after the reaction, carry out solid-liquid separation, and wash the obtained solid product with an appropriate amount of deionized water Wash until the centrifugal supernatant satisfies pH>5, and dry the washed solid product in an oven at 80° C. for 12 hours, and grind to obtain a white powder of zirconium phosphate.
以下实施例中，采用的分散剂为润湿分散剂5040，消泡剂为有机硅消泡剂470。In the following examples, the dispersant used is wetting and dispersing agent 5040, and the defoamer is silicone defoamer 470.
以下实施例中，采用的甲基丙烯酸改性丙烯酸酯乳液的制备方法包括如下步骤：In the following examples, the preparation method of the methacrylic acid-modified acrylate emulsion that adopts comprises the steps:
1)将2.0g烷基酚聚氧乙烯醚和4.0g十二烷基硫酸钠溶于90ml去离子水中配制成乳化剂水溶液，并将其分为35ml、30ml、25ml三份；将35ml乳化剂水溶液中加入100g丙烯酸正丁酯和20g甲基丙烯酸甲酯，在室温下搅拌混合，预乳化1h，制得核预乳化液；在30ml乳化剂水溶液中加入20g丙烯酸正丁酯、60g甲基丙烯酸甲酯和4.8g甲基丙烯酸，在室温下搅拌混合，预乳化2h，制得壳预乳化液；将0.6g碳酸氢钠溶于25ml乳化剂水溶液中搅拌溶解，制得缓冲剂水溶液；将1.0g过硫酸钾加入到30ml去离子水中搅拌溶解，制得引发剂水溶液；1) Dissolve 2.0g of alkylphenol polyoxyethylene ether and 4.0g of sodium lauryl sulfate in 90ml of deionized water to prepare an emulsifier aqueous solution, and divide it into three parts of 35ml, 30ml, and 25ml; Add 100g of n-butyl acrylate and 20g of methyl methacrylate to the aqueous solution, stir and mix at room temperature, and pre-emulsify for 1 hour to obtain a nuclear pre-emulsion; add 20g of n-butyl acrylate, 60g of methacrylic acid Methyl ester and 4.8g of methacrylic acid were stirred and mixed at room temperature, and pre-emulsified for 2 hours to obtain a shell pre-emulsion; 0.6g of sodium bicarbonate was dissolved in 25ml of an emulsifier aqueous solution and stirred to dissolve to obtain an aqueous buffer solution; 1.0 g potassium persulfate is added to 30ml deionized water and stirred and dissolved to obtain an aqueous initiator solution;
2)种子乳液的制备：在反应容器中，边搅拌边依次加入缓冲剂水溶液、1/3体积的引发 剂水溶液和1/2体积的核预乳化液，升温至70℃，当乳液出现大量蓝光时，保温0.5h，得种子乳液；2) Preparation of seed emulsion: In the reaction vessel, add buffer aqueous solution, 1/3 volume of initiator aqueous solution and 1/2 volume of nuclear pre-emulsion in turn while stirring, and heat up to 70 ° C. When a large amount of blue light appears in the emulsion time, keep warm for 0.5h to obtain seed emulsion;
3)核层聚合：在种子乳液保温结束时，将剩余核预乳化液及1/3引发剂水溶液缓慢滴入种子乳液中，在1h内同时滴加完毕，控温到80℃，保温0.5h，得核层乳化液；3) Polymerization of the core layer: At the end of the heat preservation of the seed emulsion, slowly drop the remaining nuclear pre-emulsion and 1/3 initiator aqueous solution into the seed emulsion, and complete the dropwise addition within 1 hour, control the temperature to 80 ° C, and keep the temperature for 0.5 hours , to obtain the nuclear layer emulsion;
4)壳层聚合：在核乳化液保温结束时，滴加余下的引发剂水溶液和壳预乳化液，在1.5h内滴完，然后升温至85℃保温0.5h，然后自然冷却至40℃，调节pH值至8，过200目筛，得甲基丙烯酸改性丙烯酸酯核壳乳液。4) Shell polymerization: At the end of the heat preservation of the core emulsion, add the remaining initiator aqueous solution and shell pre-emulsion dropwise, and finish the drop within 1.5 hours, then raise the temperature to 85°C and keep it for 0.5h, and then naturally cool to 40°C. Adjust the pH value to 8 and pass through a 200-mesh sieve to obtain a methacrylic acid-modified acrylate core-shell emulsion.
实施例1Example 1
一种纳米磷酸锆基阻燃抑菌剂，其制备方法包括如下步骤：A kind of nano-zirconium phosphate-based flame retardant antibacterial agent, its preparation method comprises the steps:
1)剥离磷酸锆(ZrP)：在500ml四口烧瓶中，将0.01mol磷酸锆和300ml去离子水通过机械搅拌和超声作用使其充分分散，该过程持续30min，并保持温度为5℃，然后将100ml四丁基氢氧化铵溶液(TBA浓度为0.1mol/L)，于30min内匀速滴加到四口烧瓶中，滴完后继续超声搅拌反应2h，再将20ml浓度为14.5mol/L的浓磷酸在30min内匀速滴加到烧瓶中，反应结束后(2h)，将混合溶液通过离心进行固液分离，得到半透明凝胶沉淀并用蒸馏水洗涤；1) Stripping zirconium phosphate (ZrP): In a 500ml four-necked flask, 0.01mol zirconium phosphate and 300ml deionized water were fully dispersed by mechanical stirring and ultrasonication. This process lasted for 30min and kept the temperature at 5°C, then Add 100ml of tetrabutylammonium hydroxide solution (TBA concentration is 0.1mol/L) dropwise into the four-neck flask at a constant speed within 30min. Add it dropwise to the flask at a constant speed within 30 minutes. After the reaction (2 hours), the mixed solution is centrifuged for solid-liquid separation to obtain a translucent gel precipitate and wash it with distilled water;
2)接枝氯丙醛：将0.01mol的步骤1)所得产物与0.01mol氯丙醛分散在DMSO在50℃进行机械搅拌反应16h，离心洗涤后，干燥，得到淡黄色液体；2) Grafting of chlorpropionaldehyde: disperse 0.01mol of the product obtained in step 1) and 0.01mol of chlorpropionaldehyde in DMSO at 50°C for mechanical stirring for 16 hours, centrifuge and wash, and dry to obtain a light yellow liquid;
3)合成希夫碱：将步骤2)所得产物与0.01mol氨基咪唑分散在DMSO中，在80℃进行机械搅拌60min，然后加热至回流反应24h，反应结束后，冷却至室温，过滤，洗涤，即可得到基于纳米磷酸锆的阻燃抑菌剂。3) Synthesis of Schiff base: Disperse the product obtained in step 2) and 0.01mol aminoimidazole in DMSO, mechanically stir at 80°C for 60min, then heat to reflux for 24h, after the reaction, cool to room temperature, filter, wash, A flame retardant and antibacterial agent based on nanometer zirconium phosphate can be obtained.
实施例2Example 2
一种纳米磷酸锆基阻燃抑菌剂，其制备方法包括如下步骤：A kind of nano-zirconium phosphate-based flame retardant antibacterial agent, its preparation method comprises the steps:
1)剥离磷酸锆(ZrP)：在500ml四口烧瓶中，将0.01mol磷酸锆和300ml去离子水通过机械搅拌和超声作用使其充分分散，该过程持续30min，并保持温度为5℃，然后将100ml四丁基氢氧化铵溶液(TBA浓度为0.1mol/L)，于30min内匀速滴加到四口烧瓶中，滴完后继续超声搅拌反应2h，再将20ml浓度为14.5mol/L的浓磷酸在30min内匀速滴加到烧瓶中，反应结束后(2h)，将混合溶液通过离心进行固液分离，得到半透明凝胶沉淀并用蒸馏水洗涤；1) Stripping zirconium phosphate (ZrP): In a 500ml four-necked flask, 0.01mol zirconium phosphate and 300ml deionized water were fully dispersed by mechanical stirring and ultrasonication. This process lasted for 30min and kept the temperature at 5°C, then Add 100ml of tetrabutylammonium hydroxide solution (TBA concentration is 0.1mol/L) dropwise into the four-neck flask at a constant speed within 30min. Add it dropwise to the flask at a constant speed within 30 minutes. After the reaction (2 hours), the mixed solution is centrifuged for solid-liquid separation to obtain a translucent gel precipitate and wash it with distilled water;
2)接枝氯丙醛：将0.01mol的步骤1)所得产物与0.03mol氯丙醛分散在DMSO在80℃进行机械搅拌反应18h，离心洗涤后，干燥，得到淡黄色液体；2) Grafting of chlorpropionaldehyde: disperse 0.01mol of the product obtained in step 1) and 0.03mol of chlorpropionaldehyde in DMSO and perform a mechanical stirring reaction at 80° C. for 18 hours. After centrifugation and washing, dry to obtain a light yellow liquid;
3)合成希夫碱：将步骤2)所得产物与0.01mol氨基咪唑分散在DMSO中，在70℃进行机械搅拌90min，加热至回流反应18h，反应结束后，冷却至室温，过滤，洗涤，即可得到基于纳米磷酸锆的阻燃抑菌剂。3) Synthesis of Schiff base: Disperse the product obtained in step 2) and 0.01mol aminoimidazole in DMSO, mechanically stir at 70°C for 90min, heat to reflux for 18h, after the reaction is completed, cool to room temperature, filter, and wash, that is A flame retardant and antibacterial agent based on nano zirconium phosphate can be obtained.
应用例1Application example 1
将实施例1所得纳米磷酸锆基阻燃抑菌剂应用于制备膨胀型防火涂料，各组分及其所占质量百分比为：甲基丙烯酸改性丙烯酸酯乳液20％，聚磷酸铵36％，季戊四醇12％，三聚氰胺12％，二氧化钛3％，羟乙基纤维素0.5％，分散剂0.5％，消泡剂0.5％，正辛醇0.5％，水10％，基于纳米磷酸锆的阻燃抑菌剂5％；将称取的基于纳米磷酸锆的阻燃抑菌剂、聚磷酸铵、季戊四醇、三聚氰胺、二氧化钛、羟乙基纤维素研磨成粉状，然后加水充分研磨混合均匀；再加入消泡剂和分散剂，继续充分研磨；最后加入甲基丙烯酸改性丙烯酸酯乳液和正辛醇充分研磨混合均匀，即得所述防火涂料。The nano-zirconium phosphate-based flame retardant and antibacterial agent obtained in Example 1 is applied to the preparation of intumescent fireproof coatings. The components and their mass percentages are: 20% of methacrylic acid modified acrylate emulsion, 36% of ammonium polyphosphate, 12% pentaerythritol, 12% melamine, 3% titanium dioxide, 0.5% hydroxyethyl cellulose, 0.5% dispersant, 0.5% defoamer, 0.5% n-octanol, 10% water, flame retardant and antibacterial based on nano zirconium phosphate 5% agent; grind the weighed flame retardant and antibacterial agent based on nano-zirconium phosphate, ammonium polyphosphate, pentaerythritol, melamine, titanium dioxide, and hydroxyethyl cellulose into powder, then add water to fully grind and mix evenly; then add defoaming agent and dispersant, and continue to grind thoroughly; finally, add methacrylic acid modified acrylate emulsion and n-octanol, grind and mix well to obtain the fireproof coating.
应用例2Application example 2
将实施例1所得纳米磷酸锆基阻燃抑菌剂应用于制备膨胀型防火涂料，各组分及其所占质量百分比为：甲基丙烯酸改性丙烯酸酯乳液20％，聚磷酸铵36％，季戊四醇12％，三聚氰胺12％，二氧化钛3％，羟乙基纤维素0.5％，分散剂0.5％，消泡剂0.5％，正辛醇0.5％，水12％，基于纳米磷酸锆的阻燃抑菌剂3％；将称取的基于纳米磷酸锆的阻燃抑菌剂、聚磷酸铵、季戊四醇、三聚氰胺、二氧化钛、羟乙基纤维素研磨成粉状，然后加水充分研磨混合均匀；再加入消泡剂和分散剂，继续充分研磨；最后加入甲基丙烯酸改性丙烯酸酯乳液和正辛醇充分研磨混合均匀，即得所述防火涂料。The nano-zirconium phosphate-based flame retardant and antibacterial agent obtained in Example 1 is applied to the preparation of intumescent fireproof coatings. The components and their mass percentages are: 20% of methacrylic acid modified acrylate emulsion, 36% of ammonium polyphosphate, Pentaerythritol 12%, melamine 12%, titanium dioxide 3%, hydroxyethyl cellulose 0.5%, dispersant 0.5%, defoamer 0.5%, n-octanol 0.5%, water 12%, flame retardant and antibacterial based on nano zirconium phosphate 3%; Grind the weighed flame retardant and antibacterial agent based on nano-zirconium phosphate, ammonium polyphosphate, pentaerythritol, melamine, titanium dioxide, and hydroxyethyl cellulose into powder, then add water to fully grind and mix evenly; then add defoaming agent and dispersant, and continue to grind thoroughly; finally, add methacrylic acid modified acrylate emulsion and n-octanol, grind and mix well to obtain the fireproof coating.
应用例3Application example 3
将实施例1所得纳米磷酸锆基阻燃抑菌剂应用于制备膨胀型防火涂料，各组分及其所占质量百分比为：甲基丙烯酸改性丙烯酸酯乳液20％，聚磷酸铵36％，季戊四醇12％，三聚氰胺12％，二氧化钛3％，羟乙基纤维素0.5％，分散剂0.5％，消泡剂0.5％，正辛醇0.5％，水13％，基于纳米磷酸锆的阻燃抑菌剂2％；将称取的基于纳米磷酸锆的阻燃抑菌剂、聚磷酸铵、季戊四醇、三聚氰胺、二氧化钛、羟乙基纤维素研磨成粉状，然后加水充分研磨混合均匀；再加入消泡剂和分散剂，继续充分研磨；最后加入甲基丙烯酸改性丙烯酸酯乳液和正辛醇充分研磨混合均匀，即得所述防火涂料。The nano-zirconium phosphate-based flame retardant and antibacterial agent obtained in Example 1 is applied to the preparation of intumescent fireproof coatings. The components and their mass percentages are: 20% of methacrylic acid modified acrylate emulsion, 36% of ammonium polyphosphate, Pentaerythritol 12%, melamine 12%, titanium dioxide 3%, hydroxyethyl cellulose 0.5%, dispersant 0.5%, defoamer 0.5%, n-octanol 0.5%, water 13%, flame retardant and antibacterial based on nano zirconium phosphate 2%; Grind the weighed flame retardant and antibacterial agent based on nano-zirconium phosphate, ammonium polyphosphate, pentaerythritol, melamine, titanium dioxide, and hydroxyethyl cellulose into powder, then add water to fully grind and mix evenly; then add defoaming agent and dispersant, and continue to grind thoroughly; finally, add methacrylic acid modified acrylate emulsion and n-octanol, grind and mix well to obtain the fireproof coating.
对比例1Comparative example 1
对比例1所述防火涂料的制备方法与应用例1大致相同，不同之处在于各组分及其所占质量百分比为：甲基丙烯酸改性丙烯酸酯乳液20％，聚磷酸铵36％，季戊四醇12％，三聚氰胺12％，二氧化钛3％，羟乙基纤维素0.5％，分散剂0.5％，消泡剂0.5％，正辛醇0.5％，水15％。The preparation method of the fireproof coating described in Comparative Example 1 is roughly the same as Application Example 1, except that each component and its mass percentage are: 20% of methacrylic acid modified acrylate emulsion, 36% of ammonium polyphosphate, pentaerythritol 12%, melamine 12%, titanium dioxide 3%, hydroxyethyl cellulose 0.5%, dispersant 0.5%, defoamer 0.5%, n-octanol 0.5%, water 15%.
对比例2Comparative example 2
对比例2所述防火涂料的制备方法与应用例1大致相同，不同之处在于各组分及其所占 质量百分比为：甲基丙烯酸改性丙烯酸酯乳液20％，聚磷酸铵36％，季戊四醇12％，三聚氰胺12％，二氧化钛3％，羟乙基纤维素0.5％，分散剂0.5％，消泡剂0.5％，正辛醇0.5％，水10％，磷酸锆5％。The preparation method of the fireproof coating described in Comparative Example 2 is roughly the same as that of Application Example 1, except that each component and its mass percentage are: 20% of methacrylic acid modified acrylate emulsion, 36% of ammonium polyphosphate, pentaerythritol 12%, melamine 12%, titanium dioxide 3%, hydroxyethyl cellulose 0.5%, dispersant 0.5%, defoamer 0.5%, n-octanol 0.5%, water 10%, zirconium phosphate 5%.
对比例3Comparative example 3
对比例3所述防火涂料的制备方法与应用例1大致相同，不同之处在于各组分及其所占质量百分比为：甲基丙烯酸改性丙烯酸酯乳液20％，聚磷酸铵36％，季戊四醇12％，三聚氰胺12％，二氧化钛3％，羟乙基纤维素0.5％，分散剂0.5％，消泡剂0.5％，正辛醇0.5％，水10％，2-氨基咪唑5％。The preparation method of the fireproof coating described in Comparative Example 3 is roughly the same as that of Application Example 1, except that each component and its mass percentage are: 20% of methacrylic acid modified acrylate emulsion, 36% of ammonium polyphosphate, pentaerythritol 12%, melamine 12%, titanium dioxide 3%, hydroxyethyl cellulose 0.5%, dispersant 0.5%, defoamer 0.5%, n-octanol 0.5%, water 10%, 2-aminoimidazole 5%.
对比例4Comparative example 4
对比例4所述防火涂料的制备方法与应用例1大致相同，不同之处在于各组分及其所占质量百分比为：甲基丙烯酸改性丙烯酸酯乳液20％，聚磷酸铵36％，季戊四醇12％，三聚氰胺12％，二氧化钛3％，羟乙基纤维素0.5％，分散剂0.5％，消泡剂0.5％，正辛醇0.5％，水10％，磷酸锆与2-氨基咪唑的混合物5wt％(磷酸锆3wt％、2-氨基咪唑2wt％)。The preparation method of the fireproof coating described in Comparative Example 4 is roughly the same as that of Application Example 1, except that each component and its mass percentage are: 20% of methacrylic acid modified acrylate emulsion, 36% of ammonium polyphosphate, pentaerythritol 12%, melamine 12%, titanium dioxide 3%, hydroxyethyl cellulose 0.5%, dispersant 0.5%, defoamer 0.5%, n-octanol 0.5%, water 10%, zirconium phosphate and 2-aminoimidazole mixture 5wt % (zirconium phosphate 3wt%, 2-aminoimidazole 2wt%).
将应用例1～3和对比例1～4所得膨胀型防火涂料分别进行耐火性能测试，结果见表1。The intumescent fireproof coatings obtained in Application Examples 1 to 3 and Comparative Examples 1 to 4 were tested for their fire resistance performance, and the results are shown in Table 1.
表1应用例1～3和对比例1～4所得膨胀型防火涂料相关性能测试Table 1 Application Examples 1 to 3 and Comparative Examples 1 to 4 obtained intumescent fire retardant coatings related performance tests
Figure PCTCN2021120989-appb-000001
Figure PCTCN2021120989-appb-000001
Figure PCTCN2021120989-appb-000002
Figure PCTCN2021120989-appb-000002
上述结果表明：本发明所述基于纳米磷酸锆的阻燃抑菌剂具有较高的阻燃效率，抑菌效果优异，环保无污染，与树脂、基材等相容性好，并可有效兼顾材料的其它性能，将其应用于制备膨胀型防火涂料，可表现出耐火性能优异，抑菌性能较好，成炭性好，碳层强度高、稳定性好(存储时间长)等优点，且涉及的制备方法简单，适用领域广泛。The above results show that the flame retardant and bacteriostatic agent based on nano-zirconium phosphate of the present invention has high flame retardant efficiency, excellent bacteriostatic effect, environmental protection and pollution-free, good compatibility with resins, substrates, etc., and can effectively take into account Other properties of the material, when applied to the preparation of intumescent fireproof coatings, can show the advantages of excellent fire resistance, good antibacterial performance, good char formation, high carbon layer strength, good stability (long storage time), etc., and The involved preparation method is simple and has wide application fields.
以上所述仅为本发明的较佳实施例，并不用以限制本发明。本发明所列举的各原料都能实现本发明，以及各原料的上下限取值、区间值都能实现本发明，在此不一一列举实施例。此外，申请人需要指出的是，在本发明的精神和原则之内，可以根据上述说明加以改进或变换，所有这些改进和变换都应属于本发明所附权利要求的保护范围。The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Each raw material enumerated in the present invention can realize the present invention, and the upper and lower limit value of each raw material, interval value can realize the present invention, does not enumerate embodiment one by one here. In addition, the applicant needs to point out that within the spirit and principle of the present invention, improvements or changes can be made according to the above description, and all these improvements and changes should fall within the protection scope of the appended claims of the present invention.

Claims (10)

  1. 一种纳米磷酸锆基阻燃抑菌剂的制备方法，其特征在于，包括如下步骤：A preparation method of a nano-zirconium phosphate-based flame retardant and antibacterial agent, characterized in that it comprises the following steps:
    1)剥离磷酸锆：向磷酸锆分散液中滴加四丁基氢氧化铵，进行超声搅拌反应，然后滴加浓酸进行二次反应，进行固液分离，得半透明凝胶沉淀；1) Stripping zirconium phosphate: add tetrabutylammonium hydroxide dropwise to the zirconium phosphate dispersion, carry out ultrasonic stirring reaction, then add concentrated acid dropwise for secondary reaction, carry out solid-liquid separation, and obtain translucent gel precipitation;
    2)接枝氯丙醛：将步骤1)所得半透明凝胶沉淀与氯丙醛混合，进行搅拌反应，离心洗涤后，干燥，得淡黄色液体；2) Grafting chlorpropionaldehyde: mixing the translucent gel precipitate obtained in step 1) with chlorpropionaldehyde, stirring and reacting, centrifuging and washing, drying to obtain a light yellow liquid;
    3)合成希夫碱：将步骤2)所得淡黄色液体与氨基咪唑混合，进行机械搅拌，进行回流反应，冷却至室温，过滤，洗涤，即得所述基于纳米磷酸锆的阻燃抑菌剂。3) Synthesis of Schiff base: Mix the light yellow liquid obtained in step 2) with aminoimidazole, perform mechanical stirring, carry out reflux reaction, cool to room temperature, filter, and wash to obtain the flame retardant and antibacterial agent based on nano-zirconium phosphate .
  2. 根据权利要求1所述的制备方法，其特征在于，所述四丁基氢氧化铵溶液的浓度为0.05～10mol/L；滴加时间为30～90min；反应温度为0～20℃，超声搅拌反应时间为0.5～2h。The preparation method according to claim 1, characterized in that, the concentration of the tetrabutylammonium hydroxide solution is 0.05-10mol/L; the dropping time is 30-90min; the reaction temperature is 0-20°C, and the ultrasonic stirring reaction time It is 0.5～2h.
  3. 根据权利要求1所述的的制备方法，其特征在于，步骤1)中引入的磷酸锆与四丁基氢氧化铵的摩尔比为5:1～1:6。The preparation method according to claim 1, characterized in that the molar ratio of zirconium phosphate introduced in step 1) to tetrabutylammonium hydroxide is 5:1˜1:6.
  4. 根据权利要求1所述的制备方法，其特征在于，所述步骤1)中所述二次反应时间为0.5～3h。The preparation method according to claim 1, characterized in that, the secondary reaction time in the step 1) is 0.5-3h.
  5. 根据权利要求1所述的制备方法，其特征在于，所述步骤1)中引入的磷酸锆、步骤2)中引入的氯丙醛与步骤3)中引入的氨基咪唑的摩尔比为1:(1～8):(0.5～8)。preparation method according to claim 1, is characterized in that, the zirconium phosphate introduced in described step 1), the chloropropionaldehyde introduced in step 2) and the mol ratio of the aminoimidazole introduced in step 3) are 1:( 1～8): (0.5～8).
  6. 根据权利要求1所述的制备方法，其特征在于，步骤2)中所述搅拌反应温度为30～100℃，搅拌时间为12～24h。The preparation method according to claim 1, characterized in that the stirring reaction temperature in step 2) is 30-100° C., and the stirring time is 12-24 hours.
  7. 根据权利要求1所述的制备方法，其特征在于，步骤3)中所述的氨基咪唑为含有氨基的咪唑类衍生物。The preparation method according to claim 1, characterized in that the aminoimidazole described in step 3) is an amino-containing imidazole derivative.
  8. 根据权利要求1所述的制备方法，其特征在于，步骤3)中所述机械搅拌温度为60～120℃，机械搅拌时间为30～120min，回流反应时间为12～24h。The preparation method according to claim 1, characterized in that the mechanical stirring temperature in step 3) is 60-120° C., the mechanical stirring time is 30-120 min, and the reflux reaction time is 12-24 h.
  9. 一种权利要求1～8任一项所述制备方法制备的纳米磷酸锆基阻燃抑菌剂。A nano-zirconium phosphate-based flame-retardant and antibacterial agent prepared by the preparation method described in any one of claims 1-8.
  10. 一种利用权利要求9所述纳米磷酸锆基阻燃抑菌剂制备的膨胀型防火涂料，其特征在于，各组分及其所占质量百分比包括：甲基丙烯酸改性丙烯酸酯核壳乳液20～30％，聚磷酸铵30～36％，季戊四醇10～20％，三聚氰胺10～15％，二氧化钛1～5％，羟乙基纤维素0.5～1％，分散剂0.5～1％，消泡剂0.5～1％，正辛醇0.5～1％，纳米磷酸锆基阻燃抑菌剂1～10％，其余为水。An intumescent fireproof coating prepared by using the nano-zirconium phosphate-based flame-retardant and antibacterial agent according to claim 9, wherein each component and its mass percentage include: methacrylic acid modified acrylate core-shell emulsion 20 ~30%, ammonium polyphosphate 30~36%, pentaerythritol 10~20%, melamine 10~15%, titanium dioxide 1~5%, hydroxyethyl cellulose 0.5~1%, dispersant 0.5~1%, defoamer 0.5-1%, n-octanol 0.5-1%, nano-zirconium phosphate-based flame retardant and antibacterial agent 1-10%, and the rest is water.
PCT/CN2021/120989 2021-09-18 2021-09-27 Nano zirconium phosphate-based flame-retardant bacteriostatic agent and intumescent fireproof antibacterial coating prepared therefrom WO2023039939A1 (en)

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